Sodium Hydroxide Cerny Kurt, Bayer Mater Sodium Hydroxide 1 Science AG, Leverkusen, Germany ‘JoRGEN Brrrwsa, Bayer MaterialScience AG, Leverkusen, Germany 1. Introduction 1 2. Properties 1 2.1. Properties of Sodium Hydroxide 1 22. Properties of Sodium Hydroxide Solution 2 3. Production 4 311. Production of Sodium Hydroxide Solution 3 32, Production of Solid Sodium Hydroxide 6 1. Introduction Pare sodium hydroxide, NaOH, is a colorless solid. Ie does not occur in nature, but is manu- factured on a large scale from fairly readily ob- {ainable raw materials and is used in numerous chemical processes. Because of its corrosive ac- tion on many substances, itis known as caustic soda. Sodium hydroxide solution is one of the oldest man-made chemicals. The reaction of sodium catbonate with calcined limestone (causticization of soda) was already known in carly Affo-Oriental cultures. Alabaster vessels containing 3 % sodium hydroxide solution have been found in Egyptian tombs dating from 3rd century 8.c. near the Pyramid of Cheops. The first weitten records of caustic soda production dduring the early years a.n, came from Egypt and India, 2. Properties Because pure sodium hydroxide has abigh affin- ity for water, the physical and chemical prop- erties of the pure substance are diflicult to de- termine, Many of the data are obtainable only by extrapolating values for impure sodium hy- ddroxide, The same is true forthe concentration- 10 1002/14356007 24.348 pub? (© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 33. Forming 6 3.4. Specifications 8 35. Storage, Packaging, and ‘Transportation. 8 4. Uses 9 5. Safety Precautions 4 6. Economie Aspects un 7. References 2 ‘dependent physical properties of aqueous solu- tions of sodium hydroxide, since these solutions hhave a strong tendency toward supersaturation, 2.1, Properties of Sodium Hydroxide Some physical properties of solid sodium by- droxide are as follows: Deny hg 350 °C) Tel np olan wae fee) snare Boling post at 1 MPa 8 ced) Speciteheat pect st20°C S28 31g Chemical Properties. Pure sodium hydrox- ide is strongly hygroscopic. It dissolves in water ‘with liberation of heat and forms six defined by- drates (see Figs. 1 and 2, and Table 1). When transporting and storing sodium hydroxide so- Ition, the containers must be heated or insu- lated because the melting points of some of the hydrates are much greater than 0 °C. Inthe pres- ‘ence of moisture, NaOH reacts readily with at- ‘mospheric carbon dioxide to form sodium car- onate, Sodium hydroxide reacts with carbon monoxide under pressure and in the presence of moisture to yield sodium formate.2 Sodium Hydroxide ‘The high affinity of sodium hydroxide for wa- ter causes a reduction in water vapor pressure (€.g. 100.36 kPa for 50.3 wt % NaOH at 30°C), Sodium hydroxide is therefore a very effective ddrying agent. Itis fairly readily soluble in meth- anol and ethanol, Table fsb fhe yes of oium yoni cy Sabi ng Neon Tio Boe mae ‘SNOW a0 nie) Vie 14s SOK 2HL,O tenable) 22725" "Goublemeigpam Boling point curve Temperature, © 240 60800 NaOH concentration, Figure 1. The NeOH—H,0 system Anhydrous sodium hydroxide reacts very slowly with most substances. For example, it at- tacks many metals only slightly at room temper- ature (¢.g., Fe, Mg, Ca, and Cd). However, comro- sion rates inerease rapidly with increasing tem- perature, More noble metals such as nickel, sil- ver, gold, and platinum are attacked only slightly even when heated, especially if oxidizing atmo- spheres are excluded, Anhydrous sodium hy- droxide does not react with dry carbon dioxide. 2.2, Properties of Sodium Hydroxide Solution Physical Properties. The concentrations of the aqueous solutions in equilibrium with solid NaOH at various temperatures are given below A Ho gol. 8 Na0H-7H40 NaOH'S Ho S 1 w-NaOH- 4 Ho i sok E Na0H-35 1,0 F NagH-2H,0 5 NaoH-H,0 | J sok # tNaoH eT whe oe g/m 2 . eu z fi . Gon Eo M4 ns | BY ese g 40! 4 ow 2030 4050 60708 N20H content, %—— Figure 2. Ming diagram ofthe NeOH-#,0 system [1 ‘The heat of solution is ea, 44 kJ/mol at 18 °C. ‘The surface tension at 20°C increases from 7.46% 10"? Nim for a 3 wt% solution to 0.1 Nim for a 38 wt % solution [2]. A 1 mol % so- lution has a surface tension of 7.4310"? Nim at 20 °C, which decreases to 6.2310"? Nim at 90°C. The density of aqueous sodium hydroxide solution in the concentration range 0— 20 wt % ‘can be calculated from the formula 4 = dy (1.16027 10-2 2.511 10-Fe4 1.0222 10-7¢2)p—(1.081710-*— 9748 10-74 2.094%10-122)p2 where dy, glom® = density of solution at °C 1,°C =temperaturepiv dt, glem? NaOH/100 g solution lensity of water at °C ‘The densities of more concentrated aqueous sodium hydroxide solutions at 20 °C are as fol- lows: oH. Deny gm? so oo ‘The boiling point curve is shown in Figure 1 In the concentration range 0— 60 wt % NaOH, the boiling point increases approximately lin- early with temperature. AS gi solution of sodium hydroxide in wa- teris almost completely dissociated. Activity co- efficients are in the range a= 0.784 (0.1 M at 10°C) and a = 3.922 (15 Mat 70°C), Chemical Properties. Amphoteric metals such as zinc, aluminum, tin, and lead are at- tacked by dilue sodium hydroxide solution at room temperature. Iron, stainless steel, and nickel are fairly resistant 3. Production Sodium hydroxide is produced commercially in two forms: as 50 wt % solution (the most com- ‘mon form) and in the solid state (caustic soda) as pills, flakes, or cast shapes. 3.1. Production of Sodium Hydroxide Solution Electrolysis of Sodium Chloride. Sodium hydroxide solution is produced industrially mainly by the electrolysis of sodium chloride This yields sodium hydroxide solution, chlorine, and hydrogen in the mass ratio 1: 0.88: 0.025 in accordance with the following overall equation: 2NaCl+2 Hy0-92 NaOH+Cho + Inthe early 1980s, the membrane process was introduced, the other processes in operation at Sodium Hydroxide 3 that time being the amalgam and diaphragm pro- ‘cesses. Chlor-alkali production in 2004 was di- vided between the different processes as shown in Table 2. Membrane technology continued to gain market share in 2004, Based on announced ca- pacity changes, membrane processes will ac- ‘count for about 44 % ofthe total installed chlor- alkali capacity by 2009. Membrane technology saves approximately 30% electrical power and is the best available technique, so it will be in- creasingly used in new units, In Japan, by 1988 all plants based on the amalgam process had been cither shut down or converted to the membrane process. Some Japanese diaphragm plants were also replaced by membrane plants for reasons of both cost and quality. Details of the three electrolytic pro- ‘cosses are given in —» Chlorine. Treatment of the liquor from the electrolytic cell is shown schematically in Figure 3. In the amalgam process, sodium hydroxide solution is produced from sodium amalgam and water over a graphite catalyst at 80~ 120°C. The 50 wt % solution producedis very pure. Itis cooled, mer- ‘cury is removed by centrifugation or filtration through cartridge or pressure plate filters, and it is then sold without further treatment. In the diaphragm cell, the depleted sodium chloride solution from the anode compartment is wansferred quantitatively to the cathode com- partment, s0 that the cell liquor produced there contains ca, 18 wt% sodium chloride and 10 - 15 wt% sodium hydroxide. During evaporation to give a $0 wt% NaOH solution, all the im- purities carried over with the depleted sodium chloride solution are removed to their limiting solubility by fractional crystallization; thus the sodium chloride content ean only be reduced to a, 1 — 1.5 w0%, In the DH process of the PPG ‘Company, further purification is carried out by extraction with anhydrous liquid ammonia, This gives a product comparable to that from the amalgam process (rayon quality), but the pro- ‘cess is seldom used because of cost. This is also true of a Japanese process in which a relatively pure sodium hydroxide solution is obtained by cooling the 50 wt % diaphragm liquor and ro- ‘covering the crystals of pure NaOH . 3.5 H,0 formed, Details of the evaporation and putifica- tion processes are given in ~» Chlorine. Methods of optimizing the various evaporation systems4 Sodium Hydroxide “Tble2 Distt of eral production uname the remot wily wed pose (prensa apy 2008) verre 3 i 3 = s 4 3 [Desimemst] [Kmamea] © [Mentranse] Desompose Tee 6 OH thc [2080 SoH] = tneral use = ‘Mereury ‘Evaporation = z = al NaCl-separation ! 204 Now 50% NaOH Comercial ~[_Bxaporation (optional 99 % NaOH Figure 3. Treatment ofthe sodium hydroxide solution fom electlyss ells Steam ae Caustic feed Cooling water Coating water ==— Caustic, 50% Water return Condensed steam igure 4. Membrane ell aust evaporation (Bertams process) 2) Vacuum pump. b) Condenser e) Cauie cooler.) Fist evaporator ¢) Cass £) Second heat exchange. h) Caustic pump: ) Second evaporate.) Caustic pomp: k} Second caustic eat exchanger, First Heat exchanger, m) Ted evaporator product Commercial pump; £) Fast caustic eat exchangerused for treating liquor from the diaphragen cell ane described in [3] Tm the membrane process, a hydraulically Impermeable membrane prevents mixing of the electrolytes. This process produces a high- purity, virtually ehloride-free sodium hydroxide Solution comparable to that ofthe amalgam pro- cess. However, the chloride content increases by a factor of ca, 10 if operation of the cell is in- terrupted, due (o diffusion of CI ions through the membrane. The sulfate and chlorate present in the anolyte also affect the concentration of these impurities in the caustic liquor from the membrane cell, since the cation-selective mem- bane has an appreciable residual permeability for anions. Most membrane cells give optimum economic performance at « NaOH concentra- tion of 30-35 wt%. An ion-exchange mem- brane has now been developed that enables 50 wt % sodium hydroxide solution to be pro- duced in the cell 4], although a considerable in- czease in voltage is required. Such membranes ae viable only if steam costs are high and elec- tricity costs low (5]. The 30-33 wt% sodium hydroxide solution is usually concentrated in a (wo: or three-stage falling-film evaporator (de~ pening on steam costs and plant size) to give commercial 50 wt % solution (see Fig. 4). For athree-slage evaporator, the steam consumption 4s 0.5 t per ton NaOH (100%), and fora wo stage evaporator, 0.71 t per ton NaOH (100 %), with sodium hydroxide solution and steam in counter current flow. ‘The evaporation of membrane cell liquor (un- like that of diaphragm cell liquor) does not pro- duce any solid material that can foul the heat exchanger or erode the pipework. The pickup of metals during evaporation is ca.1 wt ppm af appropriate construction materials are used (nickel, stainless steel) The various evaporation techniques are described in 3], with special xef- exence to the concentration of membrane cell liquor. ‘As shown in Table 3, the three electrolytic processes have different energy requirements ‘The membrane process consumes the least electrical energy (2200 — 2500 kWh per ton NaOH) butrequites an additional 200-300 kW h per ton NaOH in the form of steam to pro- duce a50 wt % solution. The diaphragm process consumes less electrical energy than the amal- gam process but requites 700-900 kWh per Sodium Hydroxide 5 ton NaOH as steam for the evaporation stage and therefore has the highest total energy te- ‘quirement. Because of the high consumption of electrical ‘energy, much research has been aimed at reduc- ing the cell voltage, A ca. 1 V reduction can be achieved by using an oxygen diffusion cathode (as ina fuel cell) in the membrane cell process, although in this ease no byproduct hydrogen is produced. This technology is gaining increasing interest, Cell design, oxygen diffusion cathode, and integration of the cathode into the cell design are priority points of development. Also the in- vestigation of operation parameters and the pe~ riphery of the cells are in focus. Currently (in 2005) these cells have not been used on a pro- duction scale (7 - 9} The electrolysis of fused NaCl at 350°C with a G-Al303 diaphragm is also of interest. In laboratory-scale cells, a power consumption of 2350 KW -h per ton NaOH can be attained [10], This technique, too, has yet to be used on commercial scale Other Processes. The causticization of sodium carbonate solution is the oldest method of producing sodium hydroxide and was the only method available until the introduction of electrolysis. Altnough it had almost disap- peared from use, it is now of special interest for companies with access to synthetic sodium carbonate from the Solvay process or to natural sodium carbonate (e.g., tna, NaH(COz)2 :2 1,0). In this process, ahot, ca. 12 % solution of soditum carbonate is mixed with quicklime, The calcium carbonate that precipitates according to the equation, 1NayC0j~Ca0-+110-42NaOH+CaCOs is removed, and the ca. 12% solution of sodium hydroxide is evaporated in several stages. The impurities that precipitate, mainly NaCl and NaSOj, are filtered off. Further de- tails on the causticization of sodium carbonate are given in [11] In a combination of electrolytic and dialysis. cells, sodium salts can be split into the corre- sponding acids and alkalis, eg., NapS01+2 10-42 NsOH+,804 This reaction can be carried out in a wo- chamber cell with a cation- or anion-exchange6 Sodium Hydroxide Sean equal ° "00 = 390 Sone tala abe ula 00 WW of etic eat. membrane; in a three-chamber cell with a cation-exchange and an anion-exchange mem- borane; or in a multichamber cell with a combi- nation of eation, anion, and bipolar membranes [12-15] (> Sodium’ Sulfates, Chap. 1.4.1) However, in all industrially operated cells. the product is a dilute sodium hydroxide solution (15-30 wl %), which also contains some of the salt used as starting material. For this reason, this type of process is most suitable for treat- ing sodium-saltcontaining wastewater from pro- ceesses in which the dilute sodium hydroxide so- lution obtained can be recycled for neutraliza- tion purposes. ‘An alternative method of producing sodium hydroxide solution for small paper pulp plants, the ferrite recovery process, is described in [16] Here, waste liquor containing sodium salts and organic substances is evaporated, and the residue is mixed with Fes03 and calcined. The sodium ferrite formed is decomposed by water to give NaOH and Fe203 3.2, Production of Solid Sodium Hydroxide Solid sodium hydroxide (caustic soda) is ob- tained by evaporating sodium hydroxide so- lution until the water content is < 0.515 wt. The most efficient utilization of energy is achieved with multistage equipment. A flow di- gram of a plant constructed by Bertrams, Basel (Switzerland), is shown in Figure 5. ‘A 50 wt % solution is vacuum evaporated in 4 preconcentration unit, by using the heat of the vapor from the main concentrator, until the concentration reaches ca. 60 we%. In the sec- cond stage, a concentration of ca. 99 wt % is at- (ained by heating with a molten salt heat-trans- fer medium (NaNO3 ~ NaNOs - KNOs) at > 400°C in a falling-film evaporator. The prod- uctis fed to a flash evaporator that operates as a gaslft pump. Molten NaOH is raised by vacuum into a heated riser pipe, causing the remaining ‘water to evaporate. The rising steam bubbles lft the melt tothe highest point ofthe system, where the steam is pumped off. The almost anhydrous melt passes through a downcomer pipe into the holding vessel, from which itis pumped to the conditioning plant, The holding vessel, pumps, and pipes must be heated to prevent premature crystallization. Forming ‘When the NaOH meltis cooled and formed, both the solidification point of NaOH (322°C) and that of the monohydrate, NaOH - H,0 (62°C), -must be passed through quickly to prevent cak- ing due to unsolidiied monohydrate. Solid sodium hydroxide is supplied in the {form of lakes, prill, cast blocks, and less com- ‘monly as tablets, briquettes, or granules. Flakes hhave a bulk density of ca 0.9 Kell, a thick- ness ofca. 15 mm, anda diameter of5 ~ 20 mm, and are easily broken so that some dustis always formed on handling Pills have abulk density of > I kg/dm® and consist of spheres witha diam- ter of 0.10.8 mm (micropeills) or 05 2.5 Flakes. To produce flakes, molten NaOH is fed into a trough in which an internally cooled ‘drum rotates. The molten material solidifies on the surface of the partially immersed drum andis scraped off by a knife, which breaks up the shect of NaOH into flakes. ‘These are taken to a small intermediate storage silo and packed as soon as possible in sacks or steel drums. The materialCaustic feed =, Coating water Water return °U Condensed vapors Fuel (oil or gas) Sodium Hydroxide 7 Liquid caustic att Air Nitrogen Figure 5. High-Concenrtin uit for cate soda Rename process) 2) Vacvum pump: b) Condenser: e) Condensate pump: d) Farnace ui; e) Salt melt pump: ) Heated salt met tank: )Precon- feutttion uit: Vacuum pump) Condenser) Faling-flaconcenata,k) Mash evapeatr, 1) Heated cestc met ak tm) Caustic melt pump tends to bridge due to its particle shape, so that itcannot be stored in large silos or be transported by compressed air. Denineralized water Dry air Heating ~ alt Cages ane palletized prills Figure 6. Production of sodium hydroxide pills (Bertram process) 1) Caustic melt tank; b) Cause mel pump.) Spay tower, 4 Rotating spray system. c) Product cooler) Hlevator 2) Exhaust air wealmeat, 8) Silo.) Bagging and plete ing Prills are produced by spraying the molten material at ca, 360°C to form droplets. The spray equipment used can be nozzles (outdated), ‘or a spinning disk or basket. The finely divided ‘melt forms spheres of fairly uniform diameter due to surface tension, These are cooled to ca. 250°C as they fall down a shaft in which air flows upward, The prlls are collected in a fon- rel from which they run into a cooling drum where they are cooled to ca. 50 °C. The finished product is stored in silos (see Fig. 6). Unlike flakes, prills are free flowing. Also, they donotcake as readily and thus ean be stored in silos, transported in containers or other large vessels, or moved by compressed air, because they are almost dust free. Cast Blocks. Molten NaOH is directly cast into iron drums or similar containers. The drums are externally cooled intensively by spraying with water, so that a solid film of sodium by- droxide forms immediately on the walls of the container, preventing further contamination by the iron.8 Sodium Hydroxide Special Shapes. Tablets, pills, or pellets are produced by the droplet process. Molten NaOH drops from a special device made of silver onto a slowly rotating cooled table or conveyor belt (pill machine). The product has a very low con- {ent of metallic impurities, so that this process is especially suitable for producing small quan- tities (e.g., for analytical purposes). 3.4, Specifications A review of the grades of 50 wt % sodium hy- droxide solution produced by the various pro- cesses is given in -» Chlorine, Diaphragm liquor cannot be used in all applications (c.g. for vis- cose manufacture or various organic processes) because of the amounts of chloride, chlorate, and heavy metals present, ‘When corrosion-resistant materials are used for sodium hydroxide production (nickel and stainless steel), the pickup of metal (Ni, Fe) is 50°C or in the presence of oxygen, iron is slowly at- tacked by sodium hydroxide solution, For high-quality product (eg, with iron content < 1 mg/kg), cladding (uber or plastic coating) is required, At < 50°C the solution can be trans- ported by pipes of alkali-resstant ste or plas- tic (eg, PVC), Iron pipes are always kept fll prevent corrosion due ingress of air and conse- aqent black coloration ofthe solution, At higher temperature, coated materials such as rubber- lined steel, austenitic Cr—Ni steel (e.g., DIN 1.4541), nickel, Hypalon, epoxy resin, polypro- pylene, or glass fiber reinforced composites are suitable. In the later case, an inner lining rust be used to prevent contact between the glass fiber and the solution, Heat exchangers are usu- ally constructed of nickel, nickel alloys, or stain- less steel because of the high temperature. For ‘equipment handling highly concentrated solu- tions, nickels the most commonly used material because of its outstanding corrosion resistance. ‘Metals that have been in contact with solutions are difficult to weld, so that repairs to pipework and equipment which have carried sodium hy- droxide solutions are difficult. A comprehensive review of materials that can be used with sodium hydroxide is given in [17], Pipelines carrying 50 we % sodium hydrox- ide solution in cold regions are provided with ‘thermostatic heating. Solutions are tansported by road, rail tanker, or ship Caustic soda prills are stored in steel or stain less steel hoppers with a capacity of 30 — 50 m* ‘The hoppers have conical bases with an angle of 25° to the vertical and are provided with exter- nal hammering equipment, Even when the prod- uct is stored under dry air, a storage time of 36d should not be exceeded to ensure that the prills do not cake under their own weight Solid sodium hydroxide is usually packed in 25 = S0-kg hermetically sealed polyethylene sacks. For transport, the sacks are stacked on wooden palettes and shrink wrapped in polyethylene. ‘Caustic soda prills are also carried in 50- or 200-kg steel drums, loose in 1000-kg-capacity steel or flexible containers, or in transportable hoppers. In the closed system delivery (CSD) method of the PPG Company, containers coated with epoxy resin are transported by road and rail Pacumatic transport is carried out with dry air and causes very litte damage tothe product[ 18} 4. Uses ‘Most users of sodium hydroxide requite dilute aqueous solutions. The sodium hydroxide produced in Europe (9.86% 10" Ya NaOH) and in North America in 2004 was divided among various areas of use,Sodium Hydroxide “Table roduc qui: pia percentage sale of oa bye oy eral leer proces Amalgam Meine poner Daapgm ome Naus0e fos bani 091 ass a oot Sove0e esos N ‘002 00008 ovo 0008 ‘602-0000 He S01 ~0.0%002 Ket etic Potycarbo : peel Epichloro- E fhyarin Text = 1% % Pulp & Paper 14% Alumina 4% Soap. % organic 23% Figure 7. Demsand of odium hy drone in Europe in 2005 broken dowa by majoread wes (Source Bayer MatralSciense AG) as shown in Figure 7 and 8, More than 56 % of production is used in the chemical industry: 1) In inorganic chemistry, sodium hydroxide is used in the manufacture of sodium sats, for alkaline ore digestion, and for pH regulation. “The organic chemical industry uses sodium hhydroxide for saponification reactions, pro- ‘duction of nucleophilic anionic intermediates, ctherification and esterification, basic cataly- sis, andthe production of free organic bases. Sodium hydroxide solution is used for serub- ‘bing waste gases and neutralizing wastewater. In the paper industry (-+ Paper and Pulp, ‘Chap. 13.1,» Paper and Pulp, Chap. 13.2), sodium hydroxide solution is used for cook- ing wood (removal of lignin) 2 3) Inorganic 20% 4) The (extile industry uses sodium hydroxide solution to manufacture viscose and viscose staple fibers (-> Cellulose, Chap. 3.1). The sodium hydroxide solution used must con- tain only traces of chloride ions (rayon qual- ity). The surface of cotton can be improved by treatment with sodium hydroxide solution (mercerization) ‘Considerable quantities of sodium hydroxide are used for sodium phosphate production in the detergent industry. Soaps are manufac tured by the saponification of fats and oils with sodium hydroxide solution, and detergents are produced from organic sulfonic acids and sodium hydroxide. In the aluminum industry, sodium hydroxide is used mainly for the treatment of bauxite, 5) 610 Sodium Hydroxide vier PORES: icone reat \ a tt Pulp & Paper ee Inorganic 2% Organic 1% Figure & Demand of sodium hydroxide in North America in 2004 broken down hy major end wis (Source Rayer Maer- alSeienee AG) Asia 41% Arica 1% Midale East ie Sowjtunion ors Canada Contra! Europe an 2 Mexico 6 usa 21% Wiestern Europe 20% South America ‘* Figure 9. World production capacity of sodium hydroxide by region (ttl: 59 $57 000 in 2008) (Source Bayer Materi- alSeience AG)Sodium Hydroxide " =Chiorine_—NaOH a 15.000 = 14000 |— ya.000 12000 3997 1998 1999 2000 2001 2002 2003 2004 eat. 2005 Figure 10. U.S. production of chlorine and sodium hydroxide soluion (Source Bayer MaerialScience AG) 7) Waterworks use dilute sodium hydroxide so- lution to regenerate ion exchangers for water purification and wastewater treatment. 8) Other users of sodium hydroxide include clectroplating technology, the natural gas and petroleum industries, the glass and steel in- ddustries, and gold extraction (cyanide leach- {ng).In the food industry, sodium hydroxide is ‘used for degreasing, cleaning, and for pecling potatoes. ‘Consumption of caustic soda in pulp and pa per accounts for about one quarter of global caustic demand. The pulp and paper markets are relatively mature markets, sodemand growth vill be rather slow. The remaining 75 % of global NaOH demand is inclined to follow the health of the local manufacturing base, which is tied to the local gross domestic product (GDP). 5. Safety Precautions Because ofits strongly caustic action, all contact with sodium hydroxide during handling must be prevented by theuse of suitable protective equip- ‘ment (protective goggles, safety gloves, and, if needed, dust masks). Any clothing or shoes that come in contact with sodium hydroxide must be removed immediately and can be reused only af- (er thorough cleaning, Fist aid to affected parts of the body consists of washing with copious amounts of water, The skin can be neutralized with a dilute solution of a buffered weak acid (€.g., acetic acid —sodium acetate). For irriga- tion of the eyes, a special hygienic eyewash so- lution is used. The product poses no direct envi- ronmental risk and has therefore been removed from the list of chemicals (e.g., in the United States) whose emission must be reported to lo- cal and national environmental authorities. 6. Economic Aspects ‘Chlor—stkali plants are operated to meet chlo- rine demand: therefore outputs are typically con- nected to chlorine produetion. Clor alkali op- erating rates will be on a steady climb, as global ‘economics growth is stable Global chlorine demand is primarily driven bby production of commodities such as PVC, used, for example in construction parts, and iso- ceyanates, going into construction paris, funi- ture, shoe industry, consumer durables, and au- tomobiles. These markets follow the local GDP trend, thus more mature economies will typi- cally have a lower GDP and a lower growth in chlorine demand for these end uses. The world production capacity of sodium hy- Produetion (German 5200 000 4800 4600 ana 4200 4000 Sodium Hydroxide (Gormany 4999 2000 2001 2002 2003 2008 est. 2008 Figure 11, Sodium hyroxie production in Germany andthe United States, 1999-2005 (Soure Bayer MateralSienee AG) market for caustic soda will increase by 2.8% fon average (demand in 2004 is estimated to be approx. 51 x 10° t, 100%). Growing markets are textiles, water treatment, alumina produc- tion, and pulp and paper. In order to show the different growth rates in the USA and Germany, the development of the US market is shown in Figure 10. anda compar- {gon of the two markets in Figure 11 7. References 1 S. U. Picketting, J Chem. Soc. 63 (1893) 890. 2. Gmelin, 8ihed., System no. 21 3 S.A. MeCloney, J. W. Van Zee, Electrochem. Sec. 136 (1989) 2556 ~ 2564. C.B. Kelly, L. Walker, Staff of the Chlorine Insitute, Ine. (eds): The Second Chor Alkali ‘Symposium, World Chlor Alkali: An Industry in Transition, Proceedings, Washington, DC 1990, D.C. Brandt, per presented atthe Chlorine Institute Meeting, Washington, DC, April 1989. 6. 1 9. 10. 1 12 13. 14 15, 16. 0. 18500 18000 14500 14000 19500 33000 12500 E 3 é 5 i 12000 11500 R. Winkler, Chem Ind. 36 (1984) 152 - 155, D. Hoormann, 5, Jorissen, H. Pitter, Chem. Ing. Tech. 77 (2005), no. 9, 1363 ~ 1376. Bayer MaterialScience AG, DE 101 48 599, 2001 “Toagosei, Mitsui Chem., Kaneka, Chlorine Engineers, EP 104 1176, 1998, M. Kamaludeen ot al. Transactions of the SAEST 21 (1986) no. 1, 53— 56, Ullmann, 3rd ed, 12, pp. 659 ~ 660, S. Sridhar, Chem. Ing. Tech. 61 (1989) 428 - 409. HL v-Plessen ct al, Chem. Ing. Tech. 61 (1989) 933 -940. G. Kreysa, Chem. Ing. Tech, 62 (1990) 357 — 365. J. forisson, K. H. Simrock, J. Appl Electrochem. 24 (1991) $69 ~ 876. G. Venkota, Rao, IPPTA 24 (1987) no. 3,20 20, LK Nelson in B. 1. Moniz, W. 1 Pollock (88, Process Industries Corrosion, NACE, Houston, Tex. 1986, CSD, PPG Industries, Company Brochure, Pitsburg, Pa